JP2558165B2 - Process for producing high molecular weight polyalkylene oxide having unsaturated end groups - Google Patents
Process for producing high molecular weight polyalkylene oxide having unsaturated end groupsInfo
- Publication number
- JP2558165B2 JP2558165B2 JP1226860A JP22686089A JP2558165B2 JP 2558165 B2 JP2558165 B2 JP 2558165B2 JP 1226860 A JP1226860 A JP 1226860A JP 22686089 A JP22686089 A JP 22686089A JP 2558165 B2 JP2558165 B2 JP 2558165B2
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- polyalkylene oxide
- molecular weight
- unsaturated
- high molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は不飽和末端高分子量ポリアルキレンオキシド
の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an unsaturated terminal high molecular weight polyalkylene oxide.
［従来の技術］ 末端に不飽和基を有するポリアルキレンオキシドは，
ビニル重合における架橋剤や改質剤として有用である。[Prior Art] A polyalkylene oxide having an unsaturated group at the terminal is
It is useful as a crosslinking agent and modifier in vinyl polymerization.
また，特開昭52−73998号公報に記載されているよう
に，加水分解性基を有するヒドロシランと反応させて，
架橋性珪素基を末端に有する重合体にし，これを湿分硬
化性重合体として用いることも可能である。Further, as described in JP-A-52-73998, by reacting with hydrosilane having a hydrolyzable group,
It is also possible to use a polymer having a crosslinkable silicon group at its end and use this as a moisture-curable polymer.
このようなポリアルキレンオキシドは，分子量5000〜
20000程度の高分子量のものが望まれることが多いが，
市販のポリアルキレンオキシドではこのような高分子量
のものは得難い場合が多い。Such polyalkylene oxide has a molecular weight of 5,000-
A high molecular weight of about 20000 is often desired,
In many cases, it is difficult to obtain such a high molecular weight compound from a commercially available polyalkylene oxide.
特開昭53−134095号公報には，例えば下式にように，
末端に水酸基を有する比較的低分子量のポリアルキレン
オキシドを用い，アルカリ金属水酸化物の存在下で水酸
基をアルコキシド化した後，多価ハロゲン化合物を用い
てポリアルキレンオキシド分子を複数結合させて分子量
を増加させ，次に不飽和ハロゲン化合物を用いて末端水
酸基を不飽和基に変換する，不飽和末端高分子量ポリア
ルキレンオキシドの製造方法が記載されている。In Japanese Patent Laid-Open No. 53-134095, for example,
Using a relatively low molecular weight polyalkylene oxide having a hydroxyl group at the end, alkoxide the hydroxyl group in the presence of an alkali metal hydroxide, and then use a polyvalent halogen compound to combine multiple polyalkylene oxide molecules to increase the molecular weight. A process for the production of unsaturated terminal high molecular weight polyalkylene oxides is described, which is increased and then the terminal hydroxyl groups are converted to unsaturated groups using unsaturated halogen compounds.
同公報にはさらに，アルカリ金属水酸化物に代えて，
アルカリ金属，アルカリ金属水素化物，アルカリ金属ア
ルコキシドなどの，水と反応してアルカリ金属水酸化物
を生成するアルカリ金属化合物（以下，アルカリ金属あ
るいは水と反応してアルカリ金属水酸化物を生成するア
ルカリ金属化合物をアルコキシド化剤と略称する）を用
い，末端水酸基をアルコキシド化して反応させる方法を
開示している。このようなアルコキシド化剤を用いる
と，アルカリ金属水酸化物に比べ活性が高いので，当量
程度の量を使用するだけでアルコキシド化が十分に進行
するため，生成物の精製が容易であるという利点があ
る。しかしながら，同公報の記載に従って，アルコキシ
ド化剤を用いて，不飽和末端高分子量ポリアルキレンオ
キシドを製造しようとしても，高分子量化や不飽和化が
不十分であり，希望する反応を進行させるためには厳密
な反応条件の管理が必要であるという問題点が見い出さ
れた。 Further, in the publication, instead of the alkali metal hydroxide,
An alkali metal compound such as an alkali metal, an alkali metal hydride or an alkali metal alkoxide that reacts with water to form an alkali metal hydroxide (hereinafter, an alkali metal or an alkali that reacts with water to form an alkali metal hydroxide A metal compound is abbreviated as an alkoxide agent), and a method of reacting by alkoxidizing a terminal hydroxyl group is disclosed. The use of such an alkoxide agent has a higher activity than that of an alkali metal hydroxide, and the alkoxidation progresses sufficiently by using an equivalent amount, so that the product can be easily purified. There is. However, even if an attempt is made to produce an unsaturated terminal high molecular weight polyalkylene oxide by using an alkoxide agent according to the description of the publication, the high molecular weight and the unsaturated are insufficient, and in order to proceed the desired reaction. Was found to require strict control of reaction conditions.
［発明が解決しようとする課題］ 本発明は，生成物の精製が容易であるという利点を有
するアルコキシド化剤を用いた，水酸基末端ポリアルキ
レンオキシドから不飽和末端高分子量ポリアルキレンオ
キシドの製造方法において，容易に高分子量化や不飽和
化を進行させる方法を提供することを目的とする。[Problems to be Solved by the Invention] The present invention provides a method for producing an unsaturated terminal high-molecular weight polyalkylene oxide from a hydroxyl-terminated polyalkylene oxide using an alkoxide agent, which has the advantage that the product can be easily purified. An object of the present invention is to provide a method for easily increasing the molecular weight and desaturation.
［課題を解決するための手段］ 本発明者等は，鋭意検討の結果，上記の目的は主鎖
が，式−R1−Ｏ−（式中，−R1−は炭素数が２〜８であ
る２価のアルキレン基）で示される繰り返し単位よりな
り，末端に水酸基を有するポリアルキレンオキシドを原
料とし，これにアルカリ金属および／又は水と反応して
アルカリ金属水酸化物を生成するアルカリ金属化合物を
加えて，末端水酸基をアルカリ金属アルコキシド化し，
次に多価ハロゲン化合物と反応させてポリアルキレンオ
キシドの分子量を増加させ（第１工程），さらにこれを
不飽和ハロゲン化合物と反応させて分子鎖末端に不飽和
基を導入する（第２工程），不飽和末端高分子量ポリア
ルキレンオキシドの製造方法において，第１工程の前に
は，該ポリアルキレンオキシドの末端水酸基に対し当量
以下のアルカリ金属および／又は水と反応してアルカリ
金属水酸化物を生成するアルカリ金属化合物を加えて末
端アルコキシド化し，第２工程の前には，残存末端水酸
基に対し当量以上のアルカリ金属および／又は水と反応
してアルカリ金属水酸化物を生成するアルカリ金属化合
物を加えて，末端アルコキシド化することを特徴とする
不飽和末端高分子量ポリアルキレンオキシドの製造方法
によって解決されることを見い出した。[Means for Solving the Problems] As a result of earnest studies, the inventors of the present invention have found that the main purpose is that the main chain has the formula —R 1 —O— (in the formula, —R 1 — has a carbon number of 2 to 8). Which is a divalent alkylene group) and which has a hydroxyl group at the terminal as a raw material, and which reacts with an alkali metal and / or water to form an alkali metal hydroxide. Add a compound to convert the terminal hydroxyl groups to alkali metal alkoxides,
Then, it is reacted with a polyvalent halogen compound to increase the molecular weight of polyalkylene oxide (first step), and then this is reacted with an unsaturated halogen compound to introduce an unsaturated group at the end of the molecular chain (second step). In the method for producing an unsaturated terminal high molecular weight polyalkylene oxide, before the first step, an alkali metal hydroxide and / or water are reacted with an equivalent amount or less of the terminal hydroxyl group of the polyalkylene oxide to form an alkali metal hydroxide. An alkali metal compound is added to form an alkali metal compound, and before the second step, an alkali metal compound that reacts with an equivalent amount or more of alkali metal and / or water with respect to the residual terminal hydroxyl group to form an alkali metal hydroxide is added. In addition, it is solved by a method for producing an unsaturated terminal high molecular weight polyalkylene oxide characterized by terminal alkoxide formation. It was found to be.
本発明においては，原料ポリアルキレンオキシドの末
端水酸基のアルコキシド化を，第１工程および第２工程
の前の２回に分け，その程度を変えて行う点に特徴があ
る。The present invention is characterized in that the alkoxide of the terminal hydroxyl group of the raw material polyalkylene oxide is divided into two times before the first step and the second step and the degree thereof is changed.
この方法によれば，高分子量化や不飽和化が容易に進
行する理由は，次の様に説明できる。The reason why the high molecular weight and the desaturation easily proceed according to this method can be explained as follows.
すなわち，特開昭53−134095号公報に開示されている
方法では，その実施例にあるように，アルコキシド化は
第１工程の前で，ほぼ当量のアルカリ金属や高活性アル
カリ金属化合物のようなアルコキシド化剤を用いて１回
だけ行ている。この方法では，第１工程の反応が進行し
ても系中に水分が混入すると，アルコキシド基が水酸基
に戻って，第２工程が進行し難くなってしまう。これを
防止するためには，反応系の厳密な管理が必要になる。That is, in the method disclosed in Japanese Patent Laid-Open No. 53-134095, the alkoxidation is carried out before the first step such that almost equivalent amounts of alkali metal or highly active alkali metal compound are used, as shown in the examples. It is performed only once using an alkoxide agent. In this method, even if the reaction in the first step proceeds, if water is mixed into the system, the alkoxide group returns to a hydroxyl group, making it difficult to proceed in the second step. To prevent this, strict control of the reaction system is required.
また，第２工程を十分に進行させるために，第１工程
の前のアルコキシド化において，過剰のアルコキシド化
剤を用いると，第１工程において，例えば，次のような
反応がおこり，高分子量化が進行しなくなる。In addition, in order to allow the second step to proceed sufficiently, if an excess alkoxidizing agent is used in the alkoxidation before the first step, the following reaction occurs in the first step, for example, to increase the molecular weight. Does not progress.
本発明の方法を用いれば，上記のような欠点はなくな
り，容易に高分子量化と不飽和化が進行する。 The use of the method of the present invention eliminates the above-mentioned drawbacks and facilitates high molecular weight and desaturation.
本発明において，原料重合体としては，主鎖が本質的
に式 −R1−Ｏ−（式中，−R1−は炭素数が２〜８であ
る２価のアルキレン基）で示される繰り返し単位よりな
り，末端に水酸基を有するポリアルキレンオキシドを用
いる。R1としては炭素数２〜４のものが良く用いられ
る。In the present invention, the raw material polymer has a repeating main chain essentially represented by the formula —R 1 —O— (wherein, —R 1 — is a divalent alkylene group having 2 to 8 carbon atoms). A polyalkylene oxide composed of a unit and having a hydroxyl group at the terminal is used. As R 1 , those having 2 to 4 carbon atoms are often used.
また,R1は一部の水素原子が他の原子又は基に置換さ
れたものでも良い。このポリアルキレンオキシドの繰り
返し単位は−R1−のみでもよいが，他の繰り返し単位が
含有されていても良い。他の繰り返し単位を含む場合
は，−R1−Ｏ−で示される繰り返し単位は，重合体の50
重量％以上，特には80重量％以上存在するのが好まし
い。また，このポリアルキレンオキシドは，直鎖状のも
のであってもよく，分岐を有するものであってもよい
が，直鎖状のものを用いることが多い。Further, R 1 may be one in which some hydrogen atoms are substituted with other atoms or groups. The repeating unit of this polyalkylene oxide may be only -R 1- , but may contain other repeating units. When other repeating units are included, the repeating unit represented by -R 1 -O- is 50
It is preferably present in an amount of not less than 80% by weight, particularly not less than 80% by weight. The polyalkylene oxide may be linear or branched, but a linear one is often used.
原料ポリアルキレンオキシドの末端は水酸基である必
要があるが，全ての末端基が水酸基である必要はなく，
一部の末端基がメトキシ基やアリルオキシ基等の他の基
であっても良い。原料重合体中の水酸基の数としては，
重合体１分子当り平均1.1個以上，好ましくは1.5個以上
あれば良い。また，原料となるポリアルキレンオキシド
の重合度としては100前後のものが多い。このような原
料となるポリアルキレンオキシドの例としては，ポリオ
キシエチレングリコール，ポリオキシエチレントリオー
ル，ポリオキシエチレンテトラオール，ポリオキシプロ
ピレングリコール，ポリオキシプロピレントリオール，
ポリオキシプロピレンテトラオール，ポリオキシブチレ
ングリコール，ポリオキシテトラメチレングリコール，
ポリオキシペンタングリコール，ポリオキシヘキサング
リコール，ポリオキシヘプタングリコール，ポリオキシ
オクタングリコールなどのポリオキシアルキレンポリオ
ール類をあげることが出来る。これらの重合体は,1種単
独で，あるいは,2種以上混合して用いることが出来る。The end of the raw material polyalkylene oxide needs to be a hydroxyl group, but not all end groups need to be a hydroxyl group,
Some of the terminal groups may be other groups such as methoxy group and allyloxy group. The number of hydroxyl groups in the raw material polymer is
An average of 1.1 or more, preferably 1.5 or more per molecule of the polymer is sufficient. In addition, the polyalkylene oxide used as the raw material often has a degree of polymerization of around 100. Examples of such polyalkylene oxide as a raw material include polyoxyethylene glycol, polyoxyethylene triol, polyoxyethylene tetraol, polyoxypropylene glycol, polyoxypropylene triol,
Polyoxypropylene tetraol, polyoxybutylene glycol, polyoxytetramethylene glycol,
Examples thereof include polyoxyalkylene polyols such as polyoxypentane glycol, polyoxyhexane glycol, polyoxyheptane glycol and polyoxyoctane glycol. These polymers can be used alone or in combination of two or more.
このポリアルキレンオキシドの末端水酸基をアルコキ
シド化するために加えるアルコキシド化剤としては，ア
ルカリ金属や，水と反応してアルカリ金属水酸化物を生
成するアルカリ金属化合物を用いることが出来る。As the alkoxidizing agent added to alkoxide the terminal hydroxyl groups of the polyalkylene oxide, an alkali metal or an alkali metal compound that reacts with water to form an alkali metal hydroxide can be used.
その具体例としては,Na,Kなどのアルカリ金属;NaH,KH
などのアルカリ金属水素化物;CH3OHa,CH3OK,C2H5ONa,C2
H5OKなどのアルカリ金属アルコキシド等をあげることが
できる。Specific examples are alkali metals such as Na and K; NaH and KH.
Alkali metal hydrides such as; CH 3 OHa, CH 3 OK, C 2 H 5 ONa, C 2
Alkali metal alkoxides such as H 5 OK can be mentioned.
これらの中で，アルカリ金属アルコキシドが溶液とし
て用いることが出来るうえ，水素などの可燃性気体を発
生しないという点から好ましい。アルカリ金属アルコキ
シドの溶媒としては，メタノール，エタノールなどのア
ルコールを用いることができる。Among these, alkali metal alkoxides are preferable because they can be used as a solution and do not generate combustible gas such as hydrogen. As a solvent for the alkali metal alkoxide, alcohol such as methanol or ethanol can be used.
第１工程の前に行われるアルコキシド化において，ア
ルコキシド化剤は原料重合体中の水酸基に対し当量以
下，好ましくは80〜100当量％が用いられる。系中に水
分等が存在する場合には，この水分等との反応によりア
ルコキシド化剤が消費されるが，このような場合は，勿
論，アルコキシド化剤をさらに過剰に加える必要があ
る。In the alkoxidation performed before the first step, the alkoxidizing agent is used in an equivalent amount or less, preferably 80 to 100 equivalent% based on the hydroxyl group in the raw material polymer. When water or the like exists in the system, the alkoxide agent is consumed by the reaction with the water or the like. In such a case, of course, it is necessary to further add the alkoxide agent.
要は，第１工程の前に，過剰のアルコキシド化剤が系
中に存在しないことである。勿論，本発明の目的が達成
される限り，僅かに過剰のアルコキシド化剤が残存する
ことは差し支えない。The point is that no excess alkoxide agent is present in the system before the first step. Of course, a slight excess of the alkoxide agent may remain as long as the object of the present invention is achieved.
アルコキシド化の反応条件については特に限定はな
く，通常の温度，圧力で良いが，アルコキシド化剤とし
てアルカリ金属アルコキシドを用いる場合は副生するア
ルコールを系外に除去するために,50℃以上，好ましく
は100〜200℃の高温と,50mmHg以下，好ましくは10mmHg
以下の減圧下において反応を行うのが好ましい。The reaction conditions for the alkoxide formation are not particularly limited, and may be ordinary temperature and pressure. However, when an alkali metal alkoxide is used as the alkoxide agent, it is preferably 50 ° C or higher in order to remove the by-product alcohol out of the system. Is a high temperature of 100-200 ℃ and 50mmHg or less, preferably 10mmHg
It is preferable to carry out the reaction under the following reduced pressure.
第１工程であるポリアルキレンオキシドの高分子量化
に使用される多価ハロゲン化合物の例としては，塩化メ
チレン，クロロホルム，四塩化炭素，臭化メチレン，沃
化メチレン，モノクロロモノブロモメタン,1,1−ジクロ
ロ−2,2−ジメチルプロパン，塩化ベンザル，臭化ベン
ザル，ビス（クロロメチル）ベンゼン，ビス（ブロモメ
チル）ベンゼン，トリス（クロロメチル）ベンゼン,4,
4′−ビス（クロロメチル）ビフェニール，ビス（クロ
ロメチル）ナフタリンなどをあげることが出来る。Examples of the polyvalent halogen compound used for the high molecular weight polyalkylene oxide in the first step include methylene chloride, chloroform, carbon tetrachloride, methylene bromide, methylene iodide, monochloromonobromomethane, 1,1 -Dichloro-2,2-dimethylpropane, benzal chloride, benzal bromide, bis (chloromethyl) benzene, bis (bromomethyl) benzene, tris (chloromethyl) benzene, 4,
4'-bis (chloromethyl) biphenyl, bis (chloromethyl) naphthalene and the like can be mentioned.
これらは,1種単独で用いても良いし,2種以上混合して
用いても良い。これらの中で，塩化メチレン，臭化メチ
レン等のハロゲンアルキレン化合物が好ましい。These may be used alone or in combination of two or more. Of these, halogen alkylene compounds such as methylene chloride and methylene bromide are preferable.
第１工程の反応条件には特に限定はなく,0〜200℃，
減圧又は常圧で行うことができる。There are no particular restrictions on the reaction conditions in the first step,
It can be performed under reduced pressure or normal pressure.
この第１工程の高分子量化により，分子量500〜5000
程度の比較的低分子量のポリアルキレンオキシドを，分
子量1000〜20000程度の高分子量にすることが出来る。Due to the high molecular weight in the first step, the molecular weight of 500-5000
A relatively low molecular weight polyalkylene oxide can be made into a high molecular weight of about 1000 to 20000.
第２工程の前で行うアルコキシド化において，使用す
るアルコキシド化剤の量は，第１工程で生成した高分子
量ポリアルキレンオキシドの末端水酸基の量と当量以上
であれば良いが，余り過剰であると後の精製工程等で副
生物の発生が多くなる。通常，末端のアルコキシド化を
終え，さらに全末端アルコキシド基に対し５〜50当量％
程度過剰のアルコキシド化剤を添加するのが好ましい。In the alkoxidation performed before the second step, the amount of the alkoxidizing agent used may be equal to or more than the amount of the terminal hydroxyl group of the high molecular weight polyalkylene oxide produced in the first step, but it is too much. The generation of by-products increases in the subsequent purification process and the like. Usually, the alkoxide conversion of the terminal ends, and 5 to 50 equivalent% based on the total terminal alkoxide groups
It is preferable to add a slight excess of the alkoxide agent.
第２工程で使用される不飽和ハロゲン化合物として
は，反応性の高い不飽和基であるビニル基を有する，式
CH2＝CH−R2−Ｘ（式中−R2−は２価の有機基,Xはハ
ロゲン原子）で示される有機ハロゲン化合物が好まし
い。このような化合物の例としては，アリルクロライ
ド，アリルブロマイド，ビニル（クロロメチル）ベンゼ
ン，アリル（クロロメチル）ベンゼン，アリル（ブロモ
メチル）ベンゼン，アリル（クロロメチル）エーテル，
アリル（クロロメトキシ）ベンゼン,1−ブテニル（クロ
ロメチル）エーテル,1−ヘキセニル（クロロメトキシ）
ベンゼン，アリルオキシ（クロロメチル）ベンゼンなど
があげられ，これらは１種単独で用いても良いし,2種以
上混合して用いても良い。The unsaturated halogen compound used in the second step has a vinyl group which is a highly reactive unsaturated group,
An organic halogen compound represented by CH 2 ═CH—R 2 —X (wherein —R 2 — is a divalent organic group and X is a halogen atom) is preferable. Examples of such compounds include allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether,
Allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy)
Examples thereof include benzene and allyloxy (chloromethyl) benzene. These may be used alone or in combination of two or more.
第２工程の反応条件には特に限定はなく，第１工程と
同様の条件を用いることが出来る。The reaction conditions in the second step are not particularly limited, and the same conditions as in the first step can be used.
第２工程が終了すると，不飽和末端高分子量ポリアル
キレンオキシドが生成する。At the end of the second step, unsaturated terminal high molecular weight polyalkylene oxide is formed.
この後は，公知の精製方法によって，生成物を単離す
ることが出来る。After this, the product can be isolated by a known purification method.
［発明の効果］ 本発明の製造方法により，例えば,5000〜20000の高分
子量であり，末端基中の不飽和基の割合が，例えば90モ
ル％以上の高含量である不飽和末端高分子量ポリアルキ
レンオキシドを容易に得ることが出来る。EFFECTS OF THE INVENTION According to the production method of the present invention, unsaturated terminal high molecular weight poly (ethylene glycol) having a high molecular weight of, for example, 5,000 to 20,000 and a high content of unsaturated groups in the terminal groups, for example, 90 mol% or more is used. The alkylene oxide can be easily obtained.
［実施例］ （実施例 １） 平均分子量が3200であり，全末端基中の水酸基の割合
が89％（残りはイソプロペニル基等の不飽和基）である
ポリオキシプロピレングリコール320g（0.10モル）を，
窒素置換された1lの攪拌機付き耐圧反応容器に入れ，続
いてナトリウムメトキシド／メタノール溶液（ナトリウ
ムメトキシドの濃度は28重量％）30.9g（溶液中のナト
リウムメトキシドは8.66g,0.16モル）を加え,130℃に昇
温し,2時間減圧脱揮し，系内が1mmHgに達した後，ジク
ロロメタン5.1g（0.06モル）を加え,130℃で４時間反応
（第１工程）を行った。第１工程前のメトキシド化にお
いて，赤外分光光度計を用い,3500cm-1付近に表れる水
酸基の吸収強度を求める事により，もとの水酸基の90％
がメトキシド化されていることが判明した。[Examples] (Example 1) 320 g (0.10 mol) of polyoxypropylene glycol having an average molecular weight of 3200 and a ratio of hydroxyl groups in all terminal groups of 89% (the rest being unsaturated groups such as isopropenyl groups). ,
Place in a pressure-resistant reaction vessel equipped with a stirrer and purged with nitrogen, and then add 30.9 g of sodium methoxide / methanol solution (concentration of sodium methoxide is 28% by weight) (sodium methoxide in the solution is 8.66 g, 0.16 mol). In addition, the temperature was raised to 130 ° C., the system was degassed under reduced pressure for 2 hours, and after the system reached 1 mmHg, 5.1 g (0.06 mol) of dichloromethane was added and the reaction was carried out at 130 ° C. for 4 hours (first step). In the methoxide conversion before the first step, by using infrared spectrophotometer, the absorption intensity of the hydroxyl group appearing at around 3500 cm -1 was calculated to obtain 90% of the original hydroxyl group.
Was found to be methoxide.
続いて，ナトリウムメトキシド／メタノール溶液（ナ
トリウムメトキシドの濃度は28重量％）10.3g（溶液中
のナトリウムメトキシドは2.89g,0.054モル）を加え,13
0℃で１時間減圧脱揮し，系内が1mmHgに達した後，アリ
ルクロライド8.0g（0.105モル）を加え,130℃で２時間
反応（第２工程）を行った。第２工程前のメトキシド化
においては0.03モルのナトリウムメトキシドが残存して
いた。Then, add 10.3 g of sodium methoxide / methanol solution (concentration of sodium methoxide is 28% by weight) (sodium methoxide in the solution is 2.89 g, 0.054 mol), and
After devolatilization under reduced pressure at 0 ° C for 1 hour and the system reached 1 mmHg, 8.0 g (0.105 mol) of allyl chloride was added, and the reaction was performed at 130 ° C for 2 hours (second step). In the methoxidation before the second step, 0.03 mol of sodium methoxide remained.
反応終了後，反応物を1000gのｎ−ヘキサンに溶解希
釈し，この溶液にケイ酸アルミニウム50gを加え,1時間
攪拌後，濾過し，濾液を蒸発させて揮発分を除去する
と，平均分子量8000のポリプロピレンオキシド重合体30
0gを得た。この重合体の末端基は，不飽和基が98％，水
酸基が２％であった。After the reaction was completed, the reaction product was dissolved and diluted in 1000 g of n-hexane, 50 g of aluminum silicate was added to this solution, and the mixture was stirred for 1 hour, filtered, and the filtrate was evaporated to remove volatile matter. Polypropylene oxide polymer 30
I got 0g. The terminal groups of this polymer were 98% unsaturated groups and 2% hydroxyl groups.
（実施例２〜５） 種々のアルコキシド化剤，多価ハロゲン化合物および
不飽和ハロゲン化合物を用い，種々の反応温度，反応時
間，反応圧力で反応をおこなった結果を第１表に示す。
第１表に示した条件以外は実施例１と同様の条件で行っ
た。(Examples 2 to 5) Table 1 shows the results of the reaction at various reaction temperatures, reaction times and reaction pressures using various alkoxide agents, polyvalent halogen compounds and unsaturated halogen compounds.
The conditions were the same as in Example 1 except for the conditions shown in Table 1.
（実施例６〜９） ポリオキシプロピレングリコールの代わりに，第２表
に示した種々のポリオキシアルキレン重合体を使用し，
第２表に示した反応条件を用い，その他の条件は実施例
１と同様に反応を行った場合の結果を第２表に示す。Examples 6 to 9 Various polyoxyalkylene polymers shown in Table 2 were used in place of polyoxypropylene glycol,
Table 2 shows the results when the reaction conditions shown in Table 2 were used and the other conditions were the same as in Example 1.
（比較例） 実施例１と同様の条件で，ポリオキシプロピレングリ
コールの水酸基と当量のナトリウムメトキシドを用い
て，第１工程の前に１回だけアルコキシド化反応を行っ
た後，分子量増大反応，末端不飽和基導入反応を続けて
行うと生成アルキレンオキシド重合体の末端不飽和基含
有量は低いものであった。(Comparative Example) Under the same conditions as in Example 1, using a hydroxyl group of polyoxypropylene glycol and an equivalent amount of sodium methoxide, an alkoxide reaction was carried out only once before the first step, followed by a molecular weight increasing reaction, When the terminal unsaturated group introduction reaction was continuously carried out, the content of terminal unsaturated groups in the produced alkylene oxide polymer was low.
Claims (9)
が２〜８である２価のアルキレン基）で示される繰り返
し単位よりなり，末端に水酸基を有するポリアルキレン
オキシドを原料とし，これにアルカリ金属および／又は
水と反応してアルカリ金属水酸化物を生成するアルカリ
金属化合物を加えて，末端水酸基をアルカリ金属アルコ
キシド化し，次に多価ハロゲン化合物と反応させてポリ
アルキレンオキシドの分子量を増加させ（第１工程），
さらにこれを不飽和ハロゲン化合物と反応させて，分子
鎖末端に不飽和基を導入する（第２工程），不飽和末端
高分子量ポリアルキレンオキシドの製造方法において，
第１工程前には該ポリアルキレンオキシドの末端水酸基
に対し，当量以下のアルカリ金属および／又は水と反応
してアルカリ金属水酸化物を生成するアルカリ金属化合
物を加えて，末端アルコキシド化をおこない，第２工程
前には，残存末端水酸基に対し，当量以上のアルカリ金
属および／又は水と反応してアルカリ金属水酸化物を生
成するアルカリ金属化合物を加えて，末端アルコキシド
化をおこなうことを特徴とする不飽和末端高分子量ポリ
アルキレンオキシドの製造方法。1. A main chain comprising a repeating unit represented by the formula: --R 1 --O-- (wherein --R 1 --is a divalent alkylene group having 2 to 8 carbon atoms) and having a hydroxyl group at the terminal. Using polyalkylene oxide as a raw material, add an alkali metal compound that reacts with alkali metal and / or water to form an alkali metal hydroxide, convert the terminal hydroxyl group into an alkali metal alkoxide, and then react with a polyvalent halogen compound. To increase the molecular weight of polyalkylene oxide (first step),
Further, by reacting this with an unsaturated halogen compound to introduce an unsaturated group at the end of the molecular chain (second step), a method for producing an unsaturated terminal high molecular weight polyalkylene oxide,
Before the first step, an alkali metal compound that reacts with an equivalent amount or less of an alkali metal and / or water to form an alkali metal hydroxide is added to the terminal hydroxyl group of the polyalkylene oxide to carry out terminal alkoxide. Before the second step, the terminal alkoxide is formed by adding an alkali metal compound that reacts with an equivalent amount or more of alkali metal and / or water to form an alkali metal hydroxide with respect to the residual terminal hydroxyl group. Method for producing unsaturated terminal high molecular weight polyalkylene oxide.
シエチレングリコール，ポリオキシエチレントリオー
ル，ポリオキシエチレンテトラオール，ポリオキシプロ
ピレングリコール，ポリオキシプロピレントリオール，
ポリオキシプロピレンテトラオール，ポリオキシブチレ
ングリコールの１種又は２種以上である請求項１記載の
不飽和末端高分子量ポリアルキレンオキシドの製造方
法。2. The raw material polyalkylene oxide is polyoxyethylene glycol, polyoxyethylene triol, polyoxyethylene tetraol, polyoxypropylene glycol, polyoxypropylene triol,
The method for producing an unsaturated terminal high molecular weight polyalkylene oxide according to claim 1, which is one kind or two or more kinds of polyoxypropylene tetraol and polyoxybutylene glycol.
求項１記載の不飽和末端高分子量ポリアルキレンオキシ
ドの製造方法。3. The method for producing an unsaturated terminal high molecular weight polyalkylene oxide according to claim 1, wherein the alkali metal is Na and / or K.
物である請求項１記載の不飽和末端高分子量ポリアルキ
レンオキシドの製造方法。4. The method for producing an unsaturated terminal high molecular weight polyalkylene oxide according to claim 1, wherein the alkali metal compound is an alkali metal hydroxide.
キシドである請求項１記載の不飽和末端高分子量ポリア
ルキレンオキシドの製造方法。5. The method for producing an unsaturated terminal high molecular weight polyalkylene oxide according to claim 1, wherein the alkali metal compound is an alkali metal alkoxide.
に溶解しているアルカリ金属アルコキシドである請求項
５記載の不飽和末端高分子量ポリアルキレンオキシドの
製造方法。6. The method for producing an unsaturated terminal high molecular weight polyalkylene oxide according to claim 5, wherein the alkali metal alkoxide is an alkali metal alkoxide dissolved in alcohol.
ン化合物である請求項１記載の不飽和末端高分子量ポリ
アルキレンオキシドの製造方法。7. The method for producing an unsaturated terminal high molecular weight polyalkylene oxide according to claim 1, wherein the polyvalent halogen compound is a dihalogen alkylene compound.
れる有機ハロゲン化合物である請求項１記載の不飽和末
端高分子量ポリアルキレンオキシドの製造方法。8. The unsaturated halogen compound is an organic halogen compound represented by the formula CH 2 ═CH—R 2 —X (wherein —R 2 — is a divalent organic group and X is a halogen atom). A method for producing the unsaturated terminal high molecular weight polyalkylene oxide described.
合物である請求項１記載の不飽和末端高分子量ポリアル
キレンオキシドの製造方法。9. The method for producing an unsaturated terminal high molecular weight polyalkylene oxide according to claim 1, wherein the unsaturated halogen compound is an allyl halogen compound.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1226860A JP2558165B2 (en) | 1989-08-31 | 1989-08-31 | Process for producing high molecular weight polyalkylene oxide having unsaturated end groups |
| AU61979/90A AU635764B2 (en) | 1989-08-31 | 1990-08-30 | Process for producing unsaturated group-terminated high- molecular weight polyalkylene oxide |
| US07/574,862 US5130413A (en) | 1989-08-31 | 1990-08-30 | Process for producing unsaturated group-terminated high-molecular weight polyalkylene oxide |
| EP19900116645 EP0415404A3 (en) | 1989-08-31 | 1990-08-30 | Process for producing unsaturated group-terminated high-molecular weight polyalkylene oxide |
| CA002024451A CA2024451A1 (en) | 1989-08-31 | 1990-08-31 | Process for producing unsaturated group-terminated high-molecular weight polyalkylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1226860A JP2558165B2 (en) | 1989-08-31 | 1989-08-31 | Process for producing high molecular weight polyalkylene oxide having unsaturated end groups |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0388825A JPH0388825A (en) | 1991-04-15 |
| JP2558165B2 true JP2558165B2 (en) | 1996-11-27 |
Family
ID=16851706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1226860A Expired - Lifetime JP2558165B2 (en) | 1989-08-31 | 1989-08-31 | Process for producing high molecular weight polyalkylene oxide having unsaturated end groups |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5130413A (en) |
| EP (1) | EP0415404A3 (en) |
| JP (1) | JP2558165B2 (en) |
| AU (1) | AU635764B2 (en) |
| CA (1) | CA2024451A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992009647A1 (en) * | 1990-11-27 | 1992-06-11 | Commonwealth Scientific And Industrial Research Organisation | Poly(alkylene) oxides |
| AU642799B2 (en) * | 1990-11-27 | 1993-10-28 | Commonwealth Scientific And Industrial Research Organisation | Poly(alkylene oxides) |
| EP0799269A1 (en) * | 1994-12-21 | 1997-10-08 | NanoSystems L.L.C. | Polyether copolymers and a process for preparing them |
| US7064179B1 (en) | 1998-09-28 | 2006-06-20 | Carlsberg A/S | Peg-based macromonomers, chemically inert polymers prepared therefrom and the use of these polymers for organic synthesis and enzyme reactions |
| US6235300B1 (en) | 1999-01-19 | 2001-05-22 | Amway Corporation | Plant protecting adjuvant containing topped or peaked alcohol alkoxylates and conventional alcohol alkoxylates |
| SE0104013L (en) * | 2001-11-30 | 2003-01-14 | Perstorp Specialty Chem Ab | Process for alkylating an alkoxylated mono-, di-, tri- or polyhydroxy compound |
| US7205337B2 (en) * | 2001-12-21 | 2007-04-17 | Isotis Orthobiologics, Inc. | End-capped polymers and compositions containing such compounds |
| DE60209795T2 (en) * | 2001-12-21 | 2006-10-05 | IsoTis Orthobiologics, Inc., Irvine | COMPOSITIONS CONTAINING END-GROUP-POLYALKYLENE GLYCOLS |
| ES2618561T3 (en) | 2010-05-27 | 2017-06-21 | Dow Global Technologies Llc | Methods for producing polyoxyalkylene polymers containing crosslinkable silyl groups |
| CN101914302B (en) * | 2010-07-17 | 2016-01-06 | 青岛大学 | A kind of K type active light-resistant red azo dye and preparation method thereof |
| CA3068866A1 (en) | 2017-06-26 | 2019-01-03 | Dow Silicones Corporation | Silicone-polyether copolymer, method of preparing same, and sealant comprising same |
| WO2020131708A2 (en) | 2018-12-21 | 2020-06-25 | Dow Silicones Corporation | Silicone-organic copolymer, sealants comprising same, and related methods |
| US11760841B2 (en) | 2018-12-21 | 2023-09-19 | Dow Silicones Corporation | Silicone-polycarbonate copolymer, sealants comprising same, and related methods |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1439577A (en) * | 1973-06-07 | 1976-06-16 | Kanegafuchi Chemical Ind | Process for preparing polyoxalkylene having allyl end-group |
| JPS53134095A (en) * | 1977-04-28 | 1978-11-22 | Kanegafuchi Chem Ind Co Ltd | Production of high-molecular weight alkylene oxide polymer |
| JPS57143324A (en) * | 1981-03-02 | 1982-09-04 | Kanegafuchi Chem Ind Co Ltd | Preparation of high-molecular weight alkylene oxide polymer |
| DE3121929C1 (en) * | 1981-06-03 | 1983-02-24 | Th. Goldschmidt Ag, 4300 Essen | Process for the preparation of polyoxyalkylene monoallyl or methallyl ethers |
| US4587365A (en) * | 1984-10-29 | 1986-05-06 | Basf Corporation | Preparing capped polyoxyalkylene polyols |
| JPH0613604B2 (en) * | 1985-03-22 | 1994-02-23 | 鐘淵化学工業株式会社 | Process for producing polyalkylene oxide containing unsaturated group at molecular end |
-
1989
- 1989-08-31 JP JP1226860A patent/JP2558165B2/en not_active Expired - Lifetime
-
1990
- 1990-08-30 US US07/574,862 patent/US5130413A/en not_active Expired - Fee Related
- 1990-08-30 EP EP19900116645 patent/EP0415404A3/en not_active Ceased
- 1990-08-30 AU AU61979/90A patent/AU635764B2/en not_active Ceased
- 1990-08-31 CA CA002024451A patent/CA2024451A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU6197990A (en) | 1991-03-07 |
| JPH0388825A (en) | 1991-04-15 |
| EP0415404A3 (en) | 1991-12-04 |
| CA2024451A1 (en) | 1991-03-01 |
| US5130413A (en) | 1992-07-14 |
| AU635764B2 (en) | 1993-04-01 |
| EP0415404A2 (en) | 1991-03-06 |
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